Hydroxyl containing copolymers

ABSTRACT

POLYMERS OF ETHYLENICALLY UNSATURATED MONOMERS, CONTAINING (A) AT LEAST 5% OF ETHYLENICALLY UNSATURATED CARBOXYLIC ACID MONOMER UNITS HAVING ACTIVE HYDROGEN ATOMS REPLACED WITH   WHERE R1 IS -CH3 AND R2 AND R3 ARE ALKYL GROUPS OF 1-12 CARBON ATOMS; AND (B) UP THROUGH 10% OF VINYL PYRROLIDONE UNITS. AND COATING COMPOSITIONS CONTAINING SUCH POLYMERS.   -C(-R1)(-R2)-R3   RADICALS, WHEREIN R IS A TERTIARY ALIPHATIC HYDROCARBON RADICAL HAVING THE STRUCTURE   -CH2-CH(-OH)-CH2-OOC-R AND/OR -CH(-CH2-OH)-CH2-OOC-R

United States Patent 3,787,519 HYDROXYL CONTAINING COPOLYMERS Joseph A.Vasta, Woodbury, N.J., assignor to E. L du Pont de Nemours and Company,Wilmington, Del. No Drawing. Original application Oct. 8, 1970, Ser. No.79,348, now Patent No. 3,679,642. Divided and this application May 11,1972, Ser. No. 252,353

Int. Cl. C08g 45/10 US. Cl. 260-834 8 Claims ABSTRACT OF THE DISCLOSUREPolymers of ethylenically unsaturated monomers, containing (A) at leastof ethylenically unsaturated carboxylic acid monomer units having activehydrogen atoms replaced with 1-12 carbon atoms; and (B) up through 10%of vinyl pyrrolidone units,

and coating compositions containing such polymers.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisionalof application Ser. No. 79,348, filed Oct. 8, 1970.

BACKGROUND OF THE INVENTION In the fabrication of home laundryappliances, flowcoating is used as a method of applying primer enamels.In this method, units are coated by simply allowing a primer enamel tofiow over them. Because of the nature of the application, the enamelmust be stable and have high solids content. Naturally, it must alsoprovide a finish with good detergent and alkali resistance.

In my US. Pat. 3,330,814 I describe and claim polymers of ethylenicallyunsaturated monomers, having an acid number of up to about 40 andcontaining at least 5% (by weight of the total polymer) of ethylenicallyunsaturated carboxylic acid monomer units having active hydrogen atomsreplaced with -R is a tertiary aliphatic hydrocarbon radical having thestructure 3,787,519 Patented Jan. 22, 1974 wherein R is CH, and R and Rare alkyl groups of 1-12 carbon atoms,

or wherein R is a tertiary aliphatic hydrocarbon radical of 8-10 carbonatoms.

These polymers, when blended with aminoplast resins and epoxy polyethercondensates, as described in column 3 line 42 ff. of my patent, can bemade into excellent appliance topcoat enamels and satisfactory flowcoatprimer enamels, although the primer enamels are subject to pigment floatand their finishes are somewhat deficient in intercoat adhesion andsometimes fail to meet the more stringent industry standards foralkaliand detergent resistance,

1 have now found that the properties of these flowcoat primers can begreatly enhanced in these respects if the film-forming polymers, asdescribed in my patent, additionally contain up to 10% (by weight),preferably about 3-8%, even more preferably about 5-6% of vinylpyrrolidone units. Under some circumstances 12% of vinyl pyrrolidoneunits will be found preferable, and under certain conditions 8-9% mayserve best.

I have also found that increasing the acid number of these polymers toabout 60 greatly increases their versatility as general film-formers.

Polymers preferred for use in my new flowcoat primer enamels are thosehaving styrene and esterified acrylic acid monomer units, as describedin column 1, line 60 ft. of my patent, and also having vinyl pyrrolidoneunits.

Polymers especially preferred contain from about 30- 77% of styreneunits, 20-69% of esterified acrylic acid units and up to 10%, preferably38% of vinyl pyrrolidone units.

The most preferred polymers contain 57-62% styrene units, 36-40%esterified acrylic acid units and 5-6% vinyl pyrrolidone units, and havean acid number of 5-20.

METHOD OF PREPARATION My new polymers are most conveniently made by themethod described in column 3, line 29 ff. of my patent and headed Method2, with the obvious addition of up to about 10% by weight of vinylpyrrolidone monomer, which in the preferred case is usually at theexpense of styrene.

These liquid polymer preparations can then be made into coatingcompositions by adding such solvents, pigments, plasticizers or fillersas are necessary, as described in my patent at column 3, line 40 if.Preferred compositions are made by adding from 5% to 30%, by weight ofthe composition, of an epoxy polyether condensate, as described incolumn 3, line 67 if. of my patent, and from 5% to by weight of thecomposition, of an aminoplast resin, as described in column 3, beginningat line 52.

The resulting compositions are usually applied by flowcoating, but canbe applied by spraying, dipping, brushing, etc., if desired. Howeverapplied, the coats are then baked at 375-425 F., preferably 400 F., forfrom about 10 to about 20 minutes to give extremely hard primer finisheswhich provide excellent adhesion between the primer and the topcoat.

It will be clear from the foregoing that all the disclosures in my US.Pat. 3,330,814 are relevant to practicing this invention, and Itherefore incorporate into this application, by reference, all thosedisclosures, including the examples. One can practice the presentinvention according to the general directions in my patent by simplykeeping in mind that the film-forming polymers disclosed there aremodified here by incorporation of up to 10% of vinyl pyrrolidone units.

3 DESCRIPTION OF THE PREFERRED EMBODIMENTS Example 1 A reactor wascharged with 5 Parts/wt.

Xylene 134 Aromatic naphtha (B.P. ISO-170 C.) 124 Cardura E 127 Thismixture was heated to reflux temperature and held there while a mixtureof Parts/wt. Styrene 260 Acrylic acid 43 Ditertiary butyl peroxide 2Vinyl pyrrolidone 23 microns.

To this mill base were then added Parts/wt. Polymer solution (as perabove) 55 Benzoguanamine-formaldehyde resin (66% solids in butanol) 53Epon 1001 1 (50% solids in 50-50 high solvency petroleumnaphtha/'butanol solution) 30 Cellosolve acetate 17 Aromatic naphtha(B.P. ISO-170 C.) 17 4o 1 Described in column 9 of U.S.P. 3,830,814.

This composition was then thinned to application viscosity andflowcoated on a washer shell, flashed for five minutes in a solventladen atmosphere and then baked 20 minutes at 400 F.

The resulting primer finish had outstanding detergent and alkaliresistance.

Example 2 A reactor was charged with Parts/Wt. Xylene 50 Cardura E 50This mixture was heated to reflux temperature and held there while amixture of Parts/wt. Styrene 48 Acrylic acid 14 Cumene hydroperoxide 3Vinyl pyrrolidone 10 Parts/wt. Rutile TiO 50 Carbon black 2 Aromaticnaphtha (B.P. -170" C.) 4 Cellosolve acetate 4 75 This mixture was sandmilled until the particles had an average diameter of 1822 microns.

To this mill base were then added Parts/wt. Polymer solution (as perabove) 60 Benzoguanamine-formaldehyde resin (66% solids in butanol) 53Epon 828 1 15 Cellosolve acetate 22 Aromatic naphtha (B.P. ISO- C.) 22Zinc octoate 1 A condensate made by reacting eplchlorohydrin anddiphenylol propane. It has a melting point of 6575 C. and an epoxyequivalent weight or 425-550. The product is sold by the Shell ChemicalCompany.

These components were thoroughly mixed, the product thinned toapplication viscosity and applied to a washer shell and baked as inExample 1.

This finish also had outstanding detergent and alkali resistance.

Other specific embodiments of my new polymers can be prepared accordingto any of Examples 1 through 9 of my patent by simply adding from about3% to about 8% (by weight) of vinyl pyrrolidone monomer to theappropriate charge. Primer compositions can be made from these polymersaccording to any of Examples 10 through 13.

I claim:

1.1 A coating composition comprising, by weight of the tota (A) 20-60%of a polymer of monoethylenically unsaturated monomers, containing (1)at least 5% (by weight of the total polymer) of ethylenicallyunsaturatedcarboxylic acid monomtgr units having active hydrogen atoms replaced W1radicals, wherein R is a tertiary aliphatic hydrocarbon radical havingthe structure where R, is -OH;, and R and R are alkyl groups of 1-12carbon atoms, and (2) 1% through 10% (by weight of the polymer) ofcopolymerizable vinyl pyrrolidone units; (B) 5-30% of an epoxy-polyethercondensate, (C) 545% of an aminoplast resin, and (D) a liquid carrier.2. A coating composition comprising, by weight of the total (A) 20-60%of a polymer of monoethylenically unsaturated monomers, containing (1)at least 5% (by weight of the total polymer) of ethylenicallyunsaturated carboxylic acid monomer units having active hydrogen atomsreplaced with and/or radicals, wherein R is a tertiary aliphatichydrocarbon group of 8-1() carbon atoms, and

(2) 1% through (by weight of the polymer) of copolymerizable vinylpyrrolidone units;

(B) 530% of an epoxy-polyether condensate,

(C) 575% of an aminoplast resin, and

(D) a liquid carrier.

3. A composition according to claim 1 wherein the monoethylenicallyunsaturated monomers in (A) are styrene, acrylic acid and vinylpyrrolidone.

4. A composition according to claim 3, wherein the polymer in (A)comprises 30% through 77% of styrene units, 20% through 69% ofesterified acrylic acid units, and 3 through 8% of vinyl pyrrolidoneunits.

5. A composition according to claim 3, wherein the polymer in (A)comprises 57 through 62% of styrene units, 36 through 40% of esterifiedacrylic acid units and 5 through 6% of vinyl pyrrolidone units.

6. A composition according to claim 2 wherein the monoethylem'callyunsaturated monomers in (A) are styrene, acrylic acid and vinylpyrrolidone.

7. A composition according to claim 2, wherein the polymer in (A)comprises through 77% of styrene units, 20% through 69% of esterifiedacrylic acid units and 3 through 8% of vinyl pyrrolidone units.

8. A composition according to claim 2, wherein the polymer in (A)comprises 57 through 62% of styrene units, from 36 through 40% ofesterified acrylic acid and 5 through 6% of vinyl pyrrolidone units.

References Cited UNITED STATES PATENTS 3,330,814 7/1967 Vasta 260-8363,366,706 1/1968 Vasta 260--834 3,600,459 8/1971 Vasta 260-834 PAULLIEBERMAN, Primary Examiner US. Cl. X.R.

26041 B, 78.5 R, 80.72, 86.1 N

